Process for making 1,3-diols from epoxides

ABSTRACT

A process for manufacturing 1,3-glycols is disclosed. The process comprises reacting an epoxide with synthesis gas in the presence of rhodium and a phosphine.

REFERENCE TO PRIOR APPLICATION

This application is a continuation-in-part of application Ser. No.898,072; filed Aug. 20, 1986, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to the manufacture of 1,3-diols from an epoxide.In one embodiment, this invention relates to the manufacture of1,3-propanediol from ethylene oxide.

Glycols in general are valuable chemical compounds which find a widevariety of utilities. Such compounds are used, for example, as chemicalintermediates in the manufacture of esters, as well as in the synthesisof polyesters. 1,3-Propanediol (1,3-PDO), also referred to as1,3-propylene glycol or trimethyleneglycol, in particular, had beenfound to be especially useful in a number of applications. Typically,1,3-propanediol has been prepared by acid-catalyzed hydration ofacrolein to form 3-hydroxypropanal which is subsequently hydrogenated tothe corresponding glycol. The high cost of acrolein and the relativelylow yields obtained in such reactions have not led to commercialprocesses for production of 1,3-propanediol which are cost competitivewith other commercially available diols which in many instances can besubstituted for 1,3-propanediol.

The preparation of 1,3-glycols by the hydroformylation of epoxides,utilizing phosphine-modified cobalt carbonyl complexes as the catalyst,is shown in U.S. Pat. No. 3,463,819. In particular, said patent showsthe production of 1,3-propanediol by hydroformylation of ethylene oxide,using a tertiary phosphine-modified cobalt carbonyl catalyst. Althoughhigh yields (92%) of 1,3-propanediol were claimed to have been producedin diethyl ether solvent, catalyst concentrations were extremely high,the amount of ethylene oxide charged was low, and no indication ofreaction times nor reaction rates was specified. This high catalystconcentration may have been necessary because of the limited catalystturn-over i.e.; 2-4 moles of product/mole of cobalt and phosphine.Yields of 1.3-propanediol were substantially lower in solvents otherthan diethyl ether.

U.S. Pat. No. 3,687,981 is also directed to a process for manufacturing1,3-propanediol. However, the process disclosed in the '981 patentemploys two separate stages. In the first stage ethylene oxide undergoesa hydroformylation reaction to produce hydroxyethyl hydroxy dioxanewhich is insoluble in the initial reaction solvent. The dioxane compoundis separated from the initial reaction solvent and is subsequentlycatalytically hydrogenated to form trimethylene glycol. The patentgenerally discusses the possibility of using as the hydroformylationreaction catalyst, transition metals, particularly those of Group VIIIof the Periodic Table, e.g., cobalt carbonyl tertiary phosphine andrhodium carbonyl. However, the examples in said patent are limited tothe use of dicobalt octacarbonyl catalyst.

U.S. Pat. No. 3,054,813 is directed toward a process for the productionof 3-hydroxyaldehydes or alpha-beta unsaturated aldehydes by thereaction of epoxides with synthesis gas. Said patent shows the use of acobalt carbonyl catalyst for the hydroformylation of ethylene oxide, butthe product which resulted was acrolein.

In an article by Yokokawa et al., Bulletin of the Chemical Society ofJapan (Vol. 37, page 677, 1964), there is shown an attempt tohydroformylate ethylene oxide and propylene oxide using a cobaltcarbonyl catalyst. In the case of ethylene oxide, the product wasoverwhelmingly composed of acetaldehyde. Small amounts of acrolein wereformed. In the case of propylene oxide, under some conditions reasonableyields of 3-hydroxybutyraldehyde were produced, but the production of1,3-butanediol is not mentioned.

It is likely that processes which produce 1,3-glycols from epoxidesusing "hydroformylation" catalysts, produce 3-hydroxyaldehydes aschemical intermediates which can either be hydrogenated to 1,3-glycolsin situ, or isolated in some manner (as in the form of theaforementioned hydroxyalkyldioxanes) and then hydrogenated in a separatestep. However, 3-hydroxyaldehydes, such as 3-hydroxypropanal, areunusually reactive species and readily undergo a variety of sidereactions. In a literature review entitled "New Synthesis With CarbonMonoxide", B. Cornils, Springer Verlag, page 131, 1980, it was statedthat numerous attempts had been made to subject oxiranes (epoxides) tothe hydroformylation reaction to produce hydroxyaldehydes and that onaccount of the greater reactivity, not only of epoxides, but also of theresulting hydroxyaldehydes, the epoxide hydroformylation generally ledto the formation of a mixture of products and thus unsatisfactoryyields.

Under the conditions of a hydroformylation reaction, isomerization ofethylene oxide to acetaldehyde (which is sometimes further hydrogenatedto ethanol) can occur. Furthermore, if hydroformylation of ethyleneoxide to 3-hydroxypropanal is successful, the 3-hydroxypropanal candehydrate to yield acrolein, which can be hydrogenated to propanal orpropanol, or the 3-hydroxypropanal can undergo condensation (aldol)reactions with other aldehyde molecules to give C₆ branched aldehydes,which can undergo dehydration and hydrogenation reactions. It istherefore highly desirable that a catalyst for the production of1,3-propanediol from ethylene oxide should be able to rapidlyhydrogenate 3-hydroxypropanal in situ before undesirable side reactionscan occur. Such a catalyst would have the economic advantage ofproducing the 1,3-propanediol product in a single reactor, without theneed for a large and expensive apparatus for the isolation andsubsequent hydrogenation of aldehydes.

Thus, there remains a need for an effective method for manufacturing1,3-glycols, especially from epoxides, which process is usable in acommercial manner.

SUMMARY OF THE INVENTION

It has now been discovered that epoxides may be converted into1,3-glycols by a hydrocarbonylation reaction which uses rhodium as thecatalyst. Thus, the present invention provides a process formanufacturing 1,3-glycols of the formula ##STR1## wherein R representshydrogen, a monovalent aliphatic or aromatic group having from one toabout twelve carbon atoms, or a divalent aliphatic group having from 4to about 6 carbon atoms which together with X forms a cyclic structure,and X represents hydrogen, or if R is divalent, a bond with R. Theprocess comprises reacting an epoxide of the formula ##STR2## wherein Rand X have the aforementioned meaning, with CO and H₂ in a suitablereaction solvent, wherein said process is characterized in that thereaction mixture contains (1) an epoxide of the foregoing structure at aconcentration from about 0.01 to about 30 weight % (2) rhodium at amolar concentration from about 0.00001 to about 0.1 molar; (3) aphosphine having the formula

    PR.sub.1 R.sub.2 R.sub.3

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of aliphatic and aromatic hydrocarbon groups, the molar ratioof rhodium to phosphine being from about 10:1 to about 1:10; (4) waterin an amount from about 0.00 to about 25 weight percent based on theweight of the reaction mixture; (5) CO; and (6) H2; wherein the molarratio of CO to H₂ is from about 10:1 to about 1:10; and (7) an acid andwherein the reaction takes place at a temperature from about 50 to about200° C. under a pressure from about 200 to about 10,000 psig, for aperiod of time which is sufficient to form at least some of the desired1,3-glycol.

Where an acid is used, it is presumed that at least some of the acid andphosphine form a salt in situ. This presumption is strengthened by thediscovery that a preformed salt of a phosphine and an acid issubstantially equivalent in the reaction of this invention.

Under the conditions in which the concentration of rhodium and phosphineare in equimolar amounts or that the molar concentration of phosphine isless than the molar concentration of rhodium, it has been found that theuse of acid is not necessary to the formation of the 1,3-glycol. Underthese conditions, acceptable yields of 1,3-propanediol (1,3-PDO) areobtained in the absence of the acid, and in some instances, the presenceof high concentrations of acid appears to decrease the rate of formationand yield of product.

In a preferred embodiment of this invention, a salt of an alkali metalcation and a solubilizing anion is also present in the reaction mixture.Typically the salt-cation to rhodium ratio is from about 20:1 to about1:20.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

As indicated above, the process of the present invention provides amethod for the manufacture of 1,3-glycols through the hydrocarbonylationof epoxides. The desired glycols therefore contain one more carbon atomand one more oxygen atom than the epoxide. Thus, for example, when theepoxide reactant is ethylene oxide, containing 2 carbon atoms, theresultant 1,3-glycol is 1,3-propanediol, containing 3 carbon atoms.Examples of other specific epoxides which are useful in the presentinvention include propylene oxide, 1,2-epoxyoctane, cyclohexene oxide,and styrene oxide.

The epoxides, as indicated previously, have the general formula ##STR3##wherein R is hydrogen, a monovalent aliphatic or aromatic group havingfrom one to about twelve carbon atoms, or a divalent aliphatic grouphaving from 4 to about 6 carbon atoms which together with X forms acyclic structure, and X represents hydrogen or, if R is divalent, a bondwith R. R therefore may be a monovalent alkyl group containing, forexample, from one to six carbon atoms or may be a divalent alkyl groupor an aromatic group, such as a phenyl group. If, for example, R is adivalent alkyl group having four carbon atoms, then the epoxide iscyclohexene oxide. The epoxide is usually present in the reactionmixture at a concentration of about 0.01 to about 30 weight percent.Typically the concentration of epoxide is from about 0.5 to 20 weightpercent.

The various epoxides may require different reaction conditions, toachieve optimum results in terms of product yield and selectivity, aswell as different specific rhodium, phosphine, or acid components. Usingthe system comprising rhodium and tricyclohexylphosphine, ethylene oxidegives good product yield and selectivity, and propylene oxide results ingood product selectivity. Cyclohexene oxide and epoxyoctane give someproducts attributable to epoxide carbonylation. Conditions for thelatter epoxides may possibly be optimized to achieve better productyield and selectivity.

The carbonylation reaction, as indicated previously, takes place in asuitable solvent. As a general principle, solvents which may becategorized as having medium to high polarity are suitable, such asaromatic solvents, ethers, polyethers, amides, sulfones, and alcohols.Depending upon the reactivity of the particular solvent selected and thespecific conditions to be employed, ketones, and esters may also beusable. The preferred solvents generally are high molecular weightethers, polyethers, and cyclic ethers, especially glycol polyethers. Anespecially preferred solvent is tetraglyme, the dimethylether oftetraethylene glycol, 2,5,8,11,14-pentaoxapentadecane. Particularlyuseful solvents also include tetrahydrofuran, diglyme, and Ucon™ oilswhich are mixed glycol polyethers of ethylene and propylene glycolsubunits.

To be suitable, a solvent should solubilize the epoxide reactant.Preferred solvents should not substantially react with any of thecomponents of the reaction mixture or the desired product. Thus, forlower molecular weight epoxides and glycols, solvents such astetraglyme, tetrahydrofuran and the like are usually used. For highermolecular weight epoxides and glycols, hydrocarbon solvents such aspetroleum ethers, toluene, and xylene may be appropriate. The lattersolvents are less suitable for lower molecular weight epoxides andglycols such as ethylene oxide and 1,3-propanediol.

The rhodium which is employed in the present process may be introducedin the form of rhodium metal, rhodium salts, and/or rhodium complexes.The only proviso is that the rhodium complex should not contain ligandswhich insolubilize or poison the catalyst. Thus, selection of theparticular rhodium component may, in part, depend upon the solubility ofthe particular rhodium metal or compound in the specific solventutilized as the reaction medium. The rhodium useful in the practice ofthe present invention includes rhodium metal, rhodium oxides, RhI₃,RhBr₃, RhCl₃, Rh(Acac)₃, Rh(CO)₂ Acac, Rh₆ (CO)₁₆, [RhCl(CO)₂ ]₂ andRh(NO₃)₃, wherein Acac represents acetylacetonate. Likewise, the rhodiumuseful in the practice of the present invention may be a rhodiumcarbonyl-phosphine complex which has been preformed, as for example asalt, prior to introduction into the reaction mixture, using anysuitable technique for preforming such complexes. The phosphine may ormay not be coordinated to the Rh. Typical of such salt-like complexes isbis-ethyltricyclohexylphosphonium hexarhodiumpentadecylcarbonyl.

The concentration of the rhodium in the reaction solvent should be inthe range from about 0.00001 molar to about 0.1 molar. Preferably, theconcentration of rhodium will be from about 0.005 to about 0.1 molar.

The phosphine which is employed in the present invention has the generalformula

    PR.sub.1 R.sub.2 R.sub.3

wherein R₁, R₂, and R₃ are all independently selected from the groupconsisting of aliphatic and aromatic radicals. Preferably, R₁, R₂, andR₃ are all alkyl groups containing from about 1 to about 12 carbonatoms. Particularly preferred alkyl groups include methyl, ethyl,n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and cyclohexyl.Aryl and mixed aryl/alkyl phosphines may be used in the presentinvention, but their efficacy is dependent upon the particular reactionconditions, including solvent, which is employed. In general, the aryland mixed aryl/alkyl phosphines are not as efficacious as thetrialkylphosphines. The most preferred phosphine istricyclohexylphosphine. Tri-iso-propylphosphine andtri-isobutylphosphine have also been found to be extremely useful.

The amount of phosphine employed is not critical, but in general, it hasbeen found that a molar ratio of rhodium to phosphine of about 1:1 ispreferred. Broadly, a range of about 10:1 to about 1:10 is operable,however. Typically, the molar ratio of rhodium to phosphine will be fromabout 4:1 to about 1:4.

Under condition where the molar concentration of phosphine is equal toor greater than the molar concentration of rhodium in the reactionmixture, it has been found desirable to add a protonic acid to thereaction mixture. Usually medium or strong acids are preferable for usein the present process. Some acids are, however, less desirable becauseof their corrosive nature or due to their insolubility in the particularsolvent. Halides in particular may promote the decomposition of ethersolvents and would be less desirable in such solvents. However, HI andHCl have been found to be extremely useful acids in the process.Preferable acids include phosphoric acid, methane sulfonic, andp-toluene sulfonic acid. Weaker acids such as acetic may be operable,depending upon the particular operating conditions, but may also becomeesterified under the conditions of the reaction. Suitable acids for theprocess of this invention include such strong acids as nitric acid,phosphoric acid, hydriodic acid, hydrochloric acid, hydrobromic acid,p-toluene sulfonic acid, and the like. Weak acids suitable for theprocess include benzoic acid, acetic acid, propionic acid, and the like.

When an acid is used, the amount of acid is desirably in approximatelyan equimolar amount with the rhodium and/or phosphine. The preferablemolar ratio of rhodium to phosphine to acid is approximately 1:1:1. As ageneral principle, it has been found that variations of the molar ratioby factors of 2-5 only result in mildly deleterious effects. Typically,the molar ratio of acid to phosphine should not be greater than 5:1.

In those instances wherein the molar ratio of phosphine to rhodium isless than 1, the presence of acid, while not causing the reaction tofail, appears to be somewhat deleterious to both the rate of formationand the yield of 1,3-glycol. Consequently, in a preferred embodiment,the presence of acid in the reaction mixture is to be avoided.

The acid may be added to the reaction mixture or a salt of the acid andphosphine may be preformed and added to or substituted for the phosphineor acid constituents in the reaction mixture.

In a preferred embodiment, metal salts, preferably salts of an alkalimetal cation, may be added to the reaction mixture. When this salt isadded it generally increases the rate of the reaction as shown by anincrease in the rate of gas up-take during the reaction. In general, thepresence of a salt also decreases the induction period of the reaction.Salt concentrations are not particularly critical to the rate or to theyield of 1,3-diol with the Rh to salt ratio being typically from about20:1 to about 1:20. Cations may include Li⁺, Na⁺, K⁺, Rb⁺, and Cs⁺. Theanions comprising the salt must be a solubilizing anions in the solventunder the conditions of the reaction. Typical anions may include F⁻,Cl⁻, Br⁻, I⁻, NO₃ ⁻, benzoate, acetate, sulfonate, and the like.

The ratio of hydrogen to carbon monoxide employed in thehydrocarbonylation reaction should be equal to or greater than 1:1 andpreferably no greater than about 5:1, although acceptable yields arerealized at concentrations in narrow ranges on both sides of thepreferred range.

With respect to the pressure employed during the hydrocarbonylationreaction, the pressure is not critical and generally falls within therange from about 200 to about 10,000 psig. Preferably, the pressurefalls in the range of from about 1,000 to about 4,000 psig.

The temperature used in the carbonylation reaction also is not critical.As a general proposition, it has been found that increasing temperaturealso increases rates. However, increasing temperatures may have anadverse affect on selectivity. Thus, some balancing of temperature isrequired in order to achieve suitable rates and suitable selectivities.Generally, a temperature of from about 50 to about 200° C. will beemployed, preferably from about 100 to about 150 ° C.

For the production of 1,3-propanediol, using the rhodium,tricyclohexylphosphine system, at 2500 psig in tetraglyme solvent,containing 0.69 M water, a temperature of 110° C. results in anefficiency of 85 to 90%, but by increasing the temperature to 130° C.,the efficiency is reduced to 70 to 75%. Also, as the temperatureincreases, the induction period also declines.

As a general proposition with respect to H₂ :CO composition, reactionpressure, and reaction temperature, all will vary somewhat based uponthe particular reaction conditions employed and adjustment thereof iswithin the ordinary skill of one in the art.

Water, in general, has been found to be useful in conjunction with manycatalysts and solvents. In particular, though the presence of water isnot necessary for the function of the catalysts used in this invention,in the absence of water, substantial induction periods are sometimesobserved between the injection of ethylene oxide and the onset of theuptake of synthesis gas and the production of product, such as1,3-propanediol. It has been found that the presence of small amounts ofwater can sometimes substantially decrease the length of the inductionperiods, and hence shorten the overall reaction times. However, if theamount of water is increased beyond a given level, poorer yields mayresult. As a broad proposition, from about 0.00 to about 25 wt. % wateris employed, preferably from about 0.0 to about 10 wt. %. The amount ofwater employed, as indicated, to achieve optimum results, will varydepending upon the particular reaction system and conditions employed.

The present invention is capable of achieving yields of 1,3-glycols,such as 1,3-propanediol in excess of 85 percent based upon the epoxide,such as ethylene oxide, and production rates substantially above 1mol/liter/hour in a single carbonylation reactor. Such results arecertainly unexpected and surprising, since the use of rhodium catalystsfor the carbonylation of epoxides to 1,3-glycols has not been shown inthe prior art. The present results are also surprising in view of thefact that most prior art cobalt catalysts generally only achievedsubstantially lower rates and efficiencies for precursors of1,3-propanediol, while the present process provides a high yields,single step process for the production of 1,3-glycols without the needfor separate, large hydrogenation reactors for 1,3-glycols precursors.

The present invention is further shown by the following nonlimitingexamples.

General Experimental Method Employed in the Examples

All examples were performed in a batch autoclave unit which consisted ofa 300 cc Hastelloy autoclave, equipped with remotely operable controlsfor feeds, vents, stirring, heating, cooling, and the like. Standardstainless-steel tubing and Swagelok fittings were employed at the lowerreactor pressures. At pressures of 2500 psig, high-pressure typefittings, valves, and tubings were employed.

All catalysts and solvents were weighed under nitrogen and rapidlycharged to a cold autoclave which was then purged twice with nitrogenand twice with synthesis gas. Subsequently, the autoclave waspressurized with synthesis gas to the desired pressure and heated underslow stirring to reaction temperature, over a period of 0.5 to 4.0hours. Ethylene oxide was then injected into the autoclave from either apressurized blowcase bomb or a Ruska syringe pump, at which time faststirring was commenced and the total reactor pressure raised to thefinal desired value, using synthesis gas to control the pressure.Constant reactor pressures were maintained automatically during the runsby feeding synthesis gas on demand from a high-pressure synthesis gasreservoir of known volume. The uptake of reaction synthesis gas wasmonitored by periodic measurement of the pressure of the synthesis gasreservoir. Runs were terminated, usually when synthesis gas uptakeslowed to nearly zero, by slowing the stirring rate, terminating thesynthesis gas feed, and cooling the reactor as rapidly as possible,typically over a 30 to 60 minute period.

Small quantities of ethylene oxide were injected into the reactor whichwas hot and pressurized, using either a Ruska syringe or a pressurizedblowcase bomb by condensation of ethylene oxide vapor, from a lecturebottle, into the blowcase bomb which was chilled to dry icetemperatures. When ethylene oxide had been charged to the blowcase bomb,the blowcase bomb was detached from the transfer apparatus, weighed,then connected to the autoclave.

When the Ruska pump method was used for injecting the ethylene oxide,liquid ethylene oxide was transferred through stainless steel lines tothe Ruska syringe pump which then injected the ethylene oxide into theautoclave unit.

Because liquid ethylene oxide became held up in the lines, fittings, andvalves leading to the autoclave, it was necessary to charge somewhatlarger than theoretical quantities of ethylene oxide to the blowcasebomb or Ruska pump and then calibrate the unit for the quantity ofethylene oxide which actually reached the autoclave. Calibration runswere performed by charging the reactor with 100 grams of water and 1.8grams of sulfuric acid and heating it to 100° C. Ethylene oxide was thencharged to the blowcase bomb or Ruska pump, injected into the reactor,which was then heated for two hours to achieve ethylene oxide hydrolysisto ethylene glycol. The resulting ethylene glycol:water solutions wereanalyze for ethylene glycol using gas chromatography. In a typical run,12.0 grams of ethylene oxide would be charged to the blowcase bomb andthe ethylene glycol equivalent of 10.0 grams of ethylene oxide reachedthe reactor. Ethylene oxide feed was then back-calculated from theethylene glycol and plots of ethylene oxide observed versus ethyleneoxide charged, were constructed. Such plots were found to be reasonablylinear over the range of 5 to 15 grams of ethylene oxide and typicallyshowed 75 to 85 percent ethylene oxide efficiency in the transferoperation. The results of such calibration runs were then used tocalculate ethylene oxide feed for the catalytic carbonylation runs.

With respect to the materials employed in the Examples, [RhCl(CO)₂ ]₂,P(C₆ H₁₁)₃ and P(n-C₄ H₉)₃ were purchased from Strem Chemicals andstored and handled under nitrogen. Rh(CO)₂ Acac was either purchasedfrom Englehard or prepared from RhCl₃ ·3H₂ O, acetylacetone, anddimethylformamide and then recrystallized from hexane to yield green-redcrystalline needles.

Ethylene oxide (99.7% min) was purchased from Matheson and stored inchilled water. H₂ /CO mixtures were purchased from Iweco. Tetraglyme andsulfolane were used in the Examples as received from Aldrich, as was then-butanol which was received from Burdick and Jackson. The toluene andtetrahydrofuran which was received from Aldrich, were distilled fromsodium metal under nitrogen.

In the following examples where yields are quoted, yields werecalculated from the observed moles of product divided by the moles of EOcalculated (via use of the EO calibration procedure) to have beencharged to the reactor. In some cases, due to some experimental error inthe ethylene oxide injection procedure and the associated calibrationprocedure, the sum of analyzed products derived from ethylene oxidesomewhat exceeded the calculated quantity of ethylene oxide charged tothe reactor. In those examples, product efficiencies (which have beennormalized to 100% EO accountability) are quoted.

EXAMPLE 1

Eighty grams of tetraglyme, 0.50 gram of Rh(CO)₂ Acac, 1.1 grams oftricyclohexylphosphine, and 0.1 gram of hydroquinone were charged to a300 cc autoclave according to standard procedures. The mixture washeated to 100° C. under 1000 psig of 2:1 H₂ /CO, the reactor pressurethen increased to 1400 psig and 8.9 grams of ethylene oxide was injectedfrom a Ruska pump. Uptake of 2:1 H₂ /CO gas began in less than 25minutes, and the pressure was thereafter maintained at approximately1400 psig by addition of 2:1 H₂ /CO on demand. The reaction wasterminated after 4.6 hours (gas adsorption had not completely ceased),and the product removed and analyzed by gas chromatography. The productcontained no free 1,3-propanediol, but did contain small amounts of3-hydroxypropanal (0.0016 mole) and 2-hydroxyethyl1,3-dioxane (0.0002mole). The major products were unconverted ethylene oxide (0.0895 mole),acrolein (0.0112 mole), and 2-methyl-pentanol (0.0097 mole). Smalleramounts of acetaldehyde, propanol, and 2-methyl pentanal were alsodetected, along with numerous other small byproducts. This exampleillustrates that ethylene oxide is carbonylated to C₃ products by theuse of Rh/phosphine catalysts in the absence of acid promoters. Onlysmall amounts "PDO-precursor" molecules were produced, but substantialamounts of C₃ products (which presumably arise from the reaction of EOwith CO and H₂) are observed. Also, substantial amounts of C₆ products(which may arise from the coupling of C₃ aldehydes) were produced.

EXAMPLE 2

Eighty grams of tetraglyme, 0.53 gram of Rh(CO)₂ Acac, 0.54 grams oftricyclohexylphosphine, 1.0 gram of 57% aqueous HI, 5.0 grams of H₂ O,and 0.1 gram of hydroquinone were charged to an autoclave and heated to120° C. under 1500 psig of 2:1 H₂ /CO. Ethylene oxide (8.9 grams) wasinjected from a Ruska pump and thereafter 2:1 H₂ /CO was fed on demandto maintain a 1500 psig pressure. The run was terminated after 116minutes. The product contained 0.057 mole of 1,3-PDO, 0.014 mole of HPA,and 0.012 mole of 2-hydroxyethyl-1,3-dioxane for a total yield of "PDOPrecursors" of 47.4%. Major byproducts included Ethanol (0.045 mole),acetaldehyde (0.019 mole), propanal (0.009 moles), propanol (0.004mole), 2-methylpentanal (0.006 mole) and 2-methylpentanol (0.005 mole).Traces of ethylene glycol and other unidentified products were alsoobserved. This example illustrates the use of an acid promoter (HI) toimprove the activity and selectivity of a rhodium/phosphine catalyst forthe carbonylation of ethylene oxide to 1,3-propanediol at relatively lowpressure.

EXAMPLE 3

Eighty grams of tetraglyme, 0.54 gram of rhodium trichloride hydrate,0.53 gram of tricyclohexylphosphine, 0.20 gram of concentrated aqueousHCl, 5.11 grams of H₂ O, and 0.11 gram of hydroquinone were charged toan autoclave. The mixture was heated to 120° C. under 1000 psig of 2:1H₂ /CO, and 9.4 grams of ethylene oxide was injected from a blowcasebomb utilizing 2:1 H₂ /CO, and the final pressure brought to 2500 psig.Gas uptake began after approximately 50 minutes, and the run wasterminated after 3 hours when gas uptake had essentially stopped. Theproduct was found to contain 0.1506 mole of 1,3-PDO and 0.006 mole ofHPA, for a combined yield of 73.4%. Major byproducts included ethanol(0.053 mole), propanol (0.017 mole), ethylene glycol (0.013 mole) andethylene oxide (0.003 mole). Because the apparent yield of EO derivedmolecules was 114.5%, the ethylene oxide efficiencies were normalized,and showed that "PDO Precursors" were formed with a 64.9% efficiency ata rate of 0.626 moles/liter/hour. This example illustrates that1,3-propanediol can be produced in reasonably good efficiency from acatalyst precursor which does not contain acetylacetonate ligands. Italso illustrates the use of hydrochloric acid promoter.

EXAMPLE 4

Eighty grams of tetraglyme, 0.51 gram of Rh(CO)₂ Acac, 0.41 gram oftri-isobutylphosphine, 0.14 gram of phosphoric acid, 5.11 gram of H₂ O,and 0.1 gram of hydroquinone were charged to an autoclave. The mixturewas heated to 120° C. under 1000 psig of 1:1 H₂ /CO, then 10.0 grams ofethylene oxide was injected from a blowcase bomb, and the pressureincreased to 2500 psig. Uptake of synthesis gas began after about 40minutes, and the run was terminated after 3.6 hours when syngas uptakehad essentially stopped. Analysis of the product showed the presence of0.166 mole of 1,3-PDO. Major byproducts included ethanol (0.0184 mole),acetaldehyde (0.0053 mole), ethylene glycol (0.012 mole), propanal(0.006 mole) and propanol (0.011 mole). The yield of 1,3 -propanediolwas 74.3% at a rate of 0.567 mole/liter/hour. This example illustratesthat 1,3-propanediol can be produced in good efficiency by use of atrialkylphosphine other than tricyclohexylphosphine.

EXAMPLE 5

Eighty grams of tetraglyme, 0.52 gram of Rh(CO)₂ Acac, 0.54 grams ofdicyclohexylphenylphosphine, 0.14 gram of phosphoric acid, 5.1 grams ofH₂ O, and 0.1 grams of hydroquinone were charged to the autoclave andheated to 110° C. under 1000 psig of 2:1 H₂ /CO. Ethylene oxide (10.1grams) was injected from a blowcase bomb, and the pressure increased to2500 psig. Gas uptake began after about 1 hour, and the run wasterminated after 6.5 hours. Analysis of the product showed the presenceof 0.115 mole of 1,3-propanediol, 0.040 mole of acetaldehyde, 0.027 moleof ethanol, and smaller amounts of acrolein, propanal, propanol, andethylene glycol. The yield of 1,3-propanediol was calculated to be 50%,at a rate of 0.22 mole/liter/hour. This example illustrates that1,3-propanediol can be produced in reasonable yields by use of a rhodiumcatalyst promoted by a phosphine which contains an aryl substituent.

EXAMPLE 6

Eighty grams of tetraglyme, 0.51 gram of Rh(CO)₂ Acac, 0.53 gram oftricyclohexylphosphine, 0.13 gram of phosphoric acid, 5.0 grams of H₂ O,and 0.1 grams of hydroquinone were charged to an autoclave and heated to110° C. under 1000 psig of 2:1 H₂ /CO. Ethylene oxide (10.2 grams) wasinjected from a blowcase bomb, and the pressure increased to 2500 psig.Gas uptake began after 50 minutes, and the run was terminated after 4.0hours. The product contained 0.1905 mole of 1,3-propanediol, 0.0235 moleof ethanol, 0.0154 mole of propanol, 0.0125 mole of ethylene glycol, and0.0089 mole of ethylene oxide. Because the apparent yield of EO derivedmolecules was 110%, the ethylene oxide based efficiencies werenormalized, and showed that 1,3-propanediol was formed with a 77.5%efficiency at a rate of 0.595 mole/liter/hour. This example illustratesthat 1,3-propanediol can be produced in relatively good efficiencies andrates by the use of a rhodium/ phosphine catalyst promoted by water andphosphoric acid.

EXAMPLE 7

Eighty grams of tetraglyme, 0.52 gram of Rh(CO)₂ Acac, 0.53 gram oftricyclohexylphosphine, 0.13 gram of phosphoric acid, 1.05 grams of H₂O, and 0.10 grams of hydroquinone were charged to an autoclave andheated to 110° C. under 1000 psig of 2:1 H₂ /CO. Ethylene oxide (10.0grams) was injected from a blowcase bomb, and the pressure increased to2500 psig. Gas uptake began after approximately 90 minutes, and the runwas terminated after 5.5 hours. The product contained 0.1931 mole of1,3-propanediol, 0.0172 mole of ethanol, 0.0141 mole of propanol, and0.0029 mole of ethylene oxide. Overall, 1,3-propanediol was produced in85% yield at a rate of 0.438 mole/liter/hour This example illustratesthat 1,3-propanediol efficiencies are somewhat improved when the amountof water is decreased relative to the levels used in previous examples.

EXAMPLE 8

Eighty grams of tetraglyme, 0.52 gram of Rh(CO)₂ Acac, 0.54 gram oftricyclohexylphosphine, 0.14 gram of phosphoric acid, and 0.10 gram ofhydroquinone were charged to the autoclave. No water was added to thecharge. The mixture was heated to 110° C. under 1000 psig of 2:1 H₂ /CO.Ethylene oxide (10.0 grams) was injected from a blowcase bomb, and thepressure increased to 2500 psig. Gas uptake began after approximately160 minutes, and the run was terminated after 6.5 hours. Productanalysis showed the presence of 0.1983 mole of 1,3-propanediol, 0.0166mole of ethanol, 0.0046 mole of acetaldehyde, and 0.0092 mole ofpropanol. The yield of 1,3-propanediol was 87% at a rate of 0.377mole/liter/hour. This example illustrates that 1,3-propanediol can beproduced in good yields in the absence of water promoter, though"induction periods" are somewhat longer in the absence of water.

EXAMPLE 9

Eighty grams of tetraglyme, 0.51 gram of Rh(CO)₂ Acac, 0.54 grams oftricyclohexylphosphine, 0.13 gram of phosphoric acid, and 1.05 grams ofH₂ O were charged to the autoclave. No hydroquinone was added. Themixture was heated to 110° C. under 1000 psig of 2:1 H₂ /CO and ethyleneoxide (10.1 grams) was injected from a blowcase bomb and the pressureincreased to 2500 psig. Gas uptake began after about 90 minutes, and therun was terminated after 6.5 hours. Product analysis showed the presenceof 0.2172 mole of 1,3-propanediol, 0.0196 mole of ethanol, 0.0133 moleof propanol, and traces of acetaldehyde and ethylene oxide. Because theapparent yield of ethylene oxide derived molecules was 113%, theethylene oxide efficiencies were normalized, and showed that1,3-propanediol was produced in 85% efficiency at a rate of 0.41mole/liter/hour. This example illustrates that the absence ofhydroquinone "promoter" (which was included in many of the examplesdocumented here) has no substantial effect on the yields or rates ofproduction of 1,3-propanediol.

EXAMPLE 10

Eighty grams of Ucon™ 50-HB-100 polyglycol ether, 0.52 gram of Rh(CO)₂Acac, 0.53 gram of tricyclohexylphosphine, 0.13 gram of phosphoric acid,5.1 grams of H₂ O, and 0.1 grams of hyroquinone were charged to theautoclave and heated to 110° C. under 1000 psig of 2:1 H₂ /CO. Ethyleneoxide (10.0 grams) was injected from a blowcase bomb, and the pressureincreased to 2500 psig. Gas uptake began after approximately 20 minutes,and the run was terminated after 3.0 hours. Product analysis showed thepresence of 0.1775 mole of 1,3-propanediol, 0.0243 mole of propanol,0.0269 mole of ethanol, 0.0125 mole of acetaldehyde, 0.0102 mole ofacrolein, and traces of ethylene oxide and ethylene glycol. Because theapparent yield of ethylene oxide derived molecules was 112%, theethylene oxide efficiencies were normalized, and showed that1,3-propanediol was produced in 70.2% efficiency, at a rate of 0.717mole/liter/hour. This example illustrates that 1,3-propanediol can beproduced in good efficiencies in a complex polyglycol ether solventother than tetraglyme.

EXAMPLE 11

Eighty grams of tetrahydrofuran, 0.52 gram of Rh(CO)₂ Acac, 0.54 gram oftricyclohexylphosphine, 0.13 gram of phosphoric acid, 5.1 grams of H₂ O,and 0.10 gram of hydroquinone were charged to the autoclave and heated110° C. under 1000 psig of 2:1 H₂ /CO. Ethylene oxide (10.0 grams) wasinjected from a blowcase bomb, and the pressure increased to 2500 psig.Gas uptake began after approximately 40 minutes, and the run wasterminated after 3.5 hours. Analysis of the product showed the presenceof 0.2058 mole of 1,3-propanediol, 0.0166 mole of ethanol, 0.114 mole ofpropanol, and 0.0026 mole of acrolein. Because the apparent yield ofethylene oxide derived molecules was 106%, the ethylene oxideefficiencies were normalized to show that 1,3-propanediol was producedin 85.8% efficiency at a rate of 0.739 mole/liter/ hour. This exampleillustrates that 1,3-propanediol can be produced in high efficiency in amonoether solvent, and that is extremely unlikely that 1,3-propanediolcould be derived from decomposition of solvent.

EXAMPLE 12

Eighty grams of tetraglyme, 0.51 gram of Rh(CO)₂ Acac, 0.54 gram oftricyclohexylphosphine, 0.14 gram of phosphoric acid, 5.11 grams of H₂O, and 0.11 gram of hydroquinone were charged to the autoclave andheated to 110° C. under 1000 psig of 2:1 H₂ /CO. Propylene oxide (15.8grams) was charged to a blowcase bomb, and then injected into theautoclave. No attempt was made to calibrate for losses of propyleneoxide during the injection procedure. No gas uptake occurred for 7.5hours, after which the reaction was halted and workup begun. The liquidproduct was recovered (101.7 grams) and analyzed by gas chromatography(GC) and GC-mass spectra. The product was found to contain approximately7.8 wt % of unconverted propylene oxide, approximately 5.5 wt %1,3-butanediol, and approximately 0.5 wt % of 1,2-propylene glycol. Noother significant products were detected. Although not optimized, thisexample illustrates that 1,3-butanediol can be produced viacarbonylation of propylene oxide in a relatively selective manner.

EXAMPLE 13

Eighty grams of tetraglyme, 0.51 gram of Rh(CO)₂ Acac, 0.55 gram oftricyclohexylphosphine, and 1 gram of water were charged to a 300 cc.autoclave according to the standard procedures. The mixture was heatedto 100° C. under 2000 psig of 2:1 H₂ /CO; the reactor pressure thenincreased to 2300 psig and 10.4 grams of ethylene oxide was injectedfrom a Ruska pump. Uptake of the 2:1 H₂ /CO gas began in about 2.16hours, and the pressure was thereafter maintained and approximately 2500psig by addition of 2:1 H₂ /CO on demand. The reactor was terminatedafter 5.5 hours and the product removed and analyzed by gaschromatography. The product contained 0.147 mole 1,3-PDO, 0.009 moleethanol, 0.032 mole propanol. This example demonstrates that an acid isnot needed to obtain good yields of 1,3-PDO when molar equivalents ofrhodium catalyst and phosphine ligand are used.

EXAMPLE 14

Eighty grams of tetraglyme, 0.51 gram of Rh(CO)₂ Acac, and 0.50 gram oftricyclohexylphosphine were charged into a 300 cc. autoclave accordingto the standard procedures. The mixture was heated to 100° C. under 2000psig of 2:1 H₂ /CO; the reactor pressure increased to 2300 psig and 10.4grams of ethylene oxide was injected from a Ruska pump. Uptake of the2:1 H₂ /CO gas began in 3 hours 10 minutes and the pressure wasthereafter maintained at approximately 2500 psig by addition of 2:1 H₂/CO on demand. The reaction was terminated at 7.5 hours and the productremoved and analyzed by gas chromatography. The product contained 0.202mole 1,3-PDO, 0.013 mole ethanol, 0.007 mole acetaldehyde, 0.007 molepropanol, and 0.007 mole propionaldehyde. This example demonstrates thatin the absence of water and an acid, a high yield of 1,3-PDO is obtainedwhen the Rh:P ratio is > 1.

EXAMPLE 15

Eighty grams of tetraglyme, 0.51 gram of Rh(CO)₂ Acac, 0.42 gram oftricyclohexylphosphine, and one gram of water were charged to a 300 cc.autoclave according to the standard procedures. The mixtures was heatedto 110° C. under 2000 psig of 2:1 H₂ /CO gas. The pressure increased to2500 psig and 10.2 grams of ethylene oxide was injected from a Ruskapump. Uptake of the gas began in about 5.33 hours, and the pressure wasthereafter maintained at approximately 2500 psig by the addition of 2:1H₂ /CO on demand. The reaction was terminated after 9.5 hours and theproduct removed and analyzed by gas chromatography. The productcontained 0.210 mole 1,3-PDO, 0.023 mole ethanol, 0.002 molesacetaldehyde, 0.009 mole propanol. This example shows that a good yieldof 1,3-PDO can be obtained at a Rh:P ratio of > 1 in the absence ofacid.

EXAMPLE 16

Eighty grams of tetraglyme, 0.51 gram Rh(CO)₂ Acac, 0.28 gram oftricyclohexylphosphine, 0.09 gram of cesium acetate, and 1 gram waterwere charged to a 300 cc autoclave according to the standard procedures.The mixture was heated to 110° C. under 2000 psig of 2:1 H₂ /CO; thereactor pressure then increased to 2300 psig and 10.2 grams of ethyleneoxide was injected from a Ruska pump. Uptake of 2:1 H₂ /CO gas began inabout one hour and the pressure was thereafter maintained at 2500 psigby the addition of 2:1 H₂ /CO gas on demand. The reaction was terminatedin 6 hours and the products removed and analyzed by gas chromatography.The product contained 0.199 mole 1,3-PDO, 0.024 mole ethanol, 0.003 moleacetaldehyde, 0.007 mole propanol, 0.002 mole propionaldehyde, plus0.0052 moles C₆ by-products. This example demonstrates the benefit ofadding a salt of an alkali metal to the reaction mixture.

EXAMPLE 17

Eighty grams of tetraglyme, 0.51 gram of Rh(CO)₂ Acac, 0.55 gram oftricyclohexylphosphine, 0.20 gram of lithium acetate, 0.16 gram ofphosphoric acid and 1 gram of water were charged into a 300 cc autoclaveaccording to the standard procedures. The mixture was heated to 110° C.under 2000 psig of 2:1 H₂ /CO; the reactor pressure increased to 2300psig; and 10.4 grams of ethylene oxide was injected from a Ruska pump.Uptake of the 2:1 H₂ /CO gas began at 1.1 hours and the pressure wasthereafter maintained at approximately 2500 psig by additions of 2:1 H₂/CO gas on demand. The reaction was terminated after 6.5 hours and theproduct removed and analyzed by gas chromatography. The productcontained 0.174 mole 1,3-PDO, 0.019 mole ethanol, 0.001 moleacetaldehyde, 0.022 mole propanol, 0.001 mole acetaldehyde, and 0.004mole of various C₆ volatile products. This example demonstrates theaddition of a salt and an acid to the reaction mixture.

EXAMPLE 18

Eighty grams of tetraglyme, 0.51 grams of Rh(CO)₂ Acac, 0.55 gram oftricyclohexylphosphine, 1.06 grams of LiI, and 0.16 grams of phosphoricacid were charged to a 300 cc autoclave according to the standardprocedures. The mixture was heated to 110° C. under 2000 psig of 2:1 H₂/CO; the reactor pressure then increased to 2300 psig and 10.4 grams ofethylene oxide was injected from a Ruska pump. Uptake of the gas beganimmediately and the pressure was thereafter maintained at 2500 psig byaddition of 2:1 H₂ /CO on demand. The reaction was terminated at 0.7hours and the products removed and analyzed by gas chromatography. Theproduct contained 0.098 mole of 1,3-PDO,0.014 mole 3-hydroxypropanal,0.059 mole of ethanol, 0.004 mole acetaldehyde, 0.006 mole of propanol,0.005 moles propionaldehyde, and lesser amounts of other volatilematerials. This example demonstrates the present invention in thepresence of a salt and an acid but in the absence of water.

EXAMPLE 19

Example 18 was repeated except that 1 gram of water was added to thereaction mixture. Products identified included 0.148 mole of 1,3-PDO,0.056 mole of ethanol, 0.002 moles acetaldehyde, 0.005 mole of propanoland several minor components. This example demonstrates the presence ofwater in the reaction mixture which includes a salt and an acid.

EXAMPLE 20

Example 18 was repeated except that 4:1 H₂ /CO was charged initially.During the progress of the reaction the pressure was maintained with 2:1H₂ /CO. The products identified in the reaction mixture were 0.099 mole1,3-PDO, 0.044 mole ethanol, 0.005 mole 3-hydroxypropanal, 0.002 moleacetaldehyde, 0.008 propanol, and lesser amounts of other products. Thisexample illustrates that a 4:1 H₂ /CO ratio is useful in the reactionalthough the ratio of 1,3-PDO to other products is not as favorable aswith a 2:1 H₂ /CO ratio.

EXAMPLE 21

Example 18 was repeated except that 1:1 H₂ /CO was charged initially.Thereafter 2:1 H₂ /CO was fed to approximate consumption. The productsidentified in the reaction mixture were 0.074 mole 1,3-PDO, 0.31 moleethanol, 0.023 mole 3-hydroxypropanal, 0.003 mole acetaldehyde, 0.007mole propionaldehyde, 0.004 mole propanol, and lesser amounts of otherproducts. This example illustrates that a 1:1 H₂ /CO ratio is useful inthe reaction, although the ratio of 1,3-PDO to other products is not asfavorable.

EXAMPLE 22

Eighty grams of tetraglyme, 0.51 gram of Rh(CO)₂ Acac, 0.55 gram oftricyclohexylphosphine, 1.06 gram of water, and 0.27 gram of 70% aqueousmethanesulfonic acid were charged into a 300 cc. autoclave according tothe standard procedure. The mixture was pressurized to 1800 psig with a2:1 H₂ /CO gas mixture at ambient room temperature and then quicklyheated to 110° C. The resultant mixture was held at this temperature andpressure (110° C. and 2165 psig) for about one hour. Ethylene oxide(11.5 grams) was pressurized into the reactor with 2500 psig 2:1 H₂ /COto initiate the reaction. The reaction was maintained at approximately110° C. and 2500 psig by heating and adding 2:1 H₂ /CO syn gas ondemand. It was terminated after 8 hours. Gas chromatographic analysis ofthe recovered product mixture contained 0.1797 mole of 1,3-PDO, 0.0082mole acetaldehyde, 0.022 mole ethanol, 0.0068 mole of ethylene glycol,0.0028 mole acrolein, and 0.0083 mole propanol. This exampledemonstrates that methanesulfonic acid is useful as an acid source inthe reaction.

EXAMPLE 23

Eighty grams of tetraglyme, 0.51 gram Rh(CO)₂ Acac, 0.41 gramtricyclohexylphosphine, 1.04 gram water, and 1.04 gram lithium iodidewere charged into an autoclave according to the standard procedure. Themixture was pressurized to 1800 psig with 2:1 H₂ /CO syn gas at ambientroom temperature and then quickly heated to 110° C. The resultantmixture was held at this condition (110° C. and 2060 psig) for about onehour. Twelve and three-tenths grams of ethylene oxide was pressurizedinto the reactor with 2500 psig 2:1 H₂ /CO to initiate the reaction. Gasuptake began immediately and the reaction temperature increasedinstantaneously from 110° to 140° C. The reaction was allowed to run for1.75 hours at approx. 110° C. and 2500 psig by heating and adding 2:1 H₂/CO on demand. Analysis of the product showed the presence of 0.0733mole of 1,3-PDO, 0.004 mole of 2-methylpentanal, 0.006 2-methylpentanol,0.0013 mole acetaldehyde, 0.0364 mole ethanol, 0.0018 mole of ethyleneglycol, 0.034 mole propionaldehyde, and 0.0143 mole propanol. Thisexample demonstrates that lithium iodide increases the reaction rate.

EXAMPLE 24

Eighty-nine grams of tetraglyme, 0.51 gram of Rh(CO)₂ Acac, 0.42 gram ofbis(l,2-dicyclohexylphospho)ethane, 1.05 gram of water, 0.23 gram of 85%aqueous phosphoric acid, and 1.04 gram lithium iodide were charged intoa 300 cc autoclave according to the standard procedure. The mixture waspressurized to 1800 psig with 2:1 H₂ /CO at ambient room temperature andquickly heated to 110° C. The resultant mixture was held at thiscondition (110° and 2125 psig) for about one hour. Twelve andthree-tenths gram of ethylene oxide was pressurized into the reactorwith 2500 psig 2:1 H₂ /CO gas to initiate the reaction. The reaction wasallowed to run for about 1.5 hours at approximately 110° C. and 2500psig by heating and adding H₂ /CO on demand. Analysis of the productshowed the presence of 0.1426 mole of 1,3-PDO, 0.001 mole of3-hydroxypropanal, 0.0003 mole of 2-methylpentanal, 0.0003 mole3-methylpentanol, 0.0007 mole acetaldehyde, 0.0908 mole ethanol, 0.002mole propionaldehyde, and 0.0088 mole propanol. This exampledemonstrates that the bidentate phosphine is similar to the monodentatephosphine in the reaction.

EXAMPLE 25

Eighty grams of tetraglyme, 0.51 gram Rh(CO)₂ Acac, 0.81 gramtricyclohexylphosphine-HI salt [HP(C₆ H₁₁)₃ ]I, and 1.064 gram waterwere charged into an autoclave according to the standard procedure. Themixture was pressurized to 1800 psig with 2:1 H₂ /CO syn gas at ambientroom temperature and then quickly heated to 110° C. The resultantmixture was held at this condition (110° C. and 2185 psig) for about onehour. Twelve and three-tenths grams of ethylene oxide was pressurizedinto the reactor with 2500 psig 2:1 H₂ /CO to initiate the reaction. Thereaction was allowed to run for 5.5 hours at approx. 110° C. and 2500psig by heating and adding 2:1 H₂ /CO on demand. Analysis of the productshowed the presence of 0.1636 mole of 1,3-PDO, 0.0024 mole of2-methylpentanal, 0.0040 mole ethylene oxide, 0.0669 mole ethanol, and0.0034 mole propanol. This example demonstrates that the phosphoniumsalt, preformed from a phosphine and an acid, is useful as a catalystpromoter in the reaction.

What is claimed is:
 1. A single-step process for manufacturing1,3-propanediolwith CO and H₂ in a ether reaction solvent, said processbeing characterized by reacting a reaction mixture comprising (1)ethylene oxide at a concentration from about 0.01 to about 30 weightpercent; (2) rhodium at a molar concentration from about 0.00001 toabout 0.1 molar; (3) a phosphine having the formula

    PR.sub.1 R.sub.2 R.sub.3                                   III

wherein R₁, R₂, and R₃ are independently selected, from the groupconsisting of aliphatic and aromatic hydrocarbon groups, the molar ratioof rhodium to phosphine being from about 10:1 to about 1:10; (4) waterin an amount up to about 25 weight percent based on the weight of thereaction mixture; (5) CO; (6) H₂ ; and (7) an acid, the molar ratio ofacid to phosphine being from about 10:1 to about 1:10; wherein the molarratio of CO to H₂ is from about 10:1 to about 1:10, and wherein thereaction takes place at a temperature from about 50 to about 200° C.under a pressure from about 200 to about 10,000 psig, for a period oftime which is sufficient to form.
 2. The process of claim 1 wherein theacid is selected from the group consisting of HI, HCl, methane sulfonicacid and phosphoric acid.
 3. The process of claim 1 wherein the solventis selected from the group consisting of tetraglyme, tetrahydrofuran,and a mixture of glycol polyethers of ethylene and propylene glycols. 4.The process of claim 2 wherein the rhodium is selected from the groupconsisting of rhodium metal, rhodium oxides, RhI₃, RhBr₃, RhCl₃,Rh(Acac)₃, Rh(CO)₂ Acac, Rh₆ (CO)₁₆, [RhCl(CO)₂ ]₂, and Rh(NO₃)₃.
 5. Theprocess of claim 4 wherein the rhodium is present at a concentrationfrom about 0.005 to about 0.10 molar.
 6. The process of claim 5 whereinthe phosphine is a trialkyl phosphine.
 7. The process of claim 6 whereinthe phosphine is selected from the group consisting of tri-isopropylphosphine, tri-sec-butylphosphine, tri-isobutylphosphine,tri-n-butylphosphine, and tri-n-propyl phosphine.
 8. The process ofclaim 1 wherein the molar ratio of rhodium to phosphine is from about1:2 to about 2:1.
 9. The process of claim 8 wherein the molar ratio ofacid to phosphine is from about 5:1 to about 1:5.
 10. The process ofclaim 9 wherein the ratio of H₂ :CO is from about 5:1 to about 1:1. 11.The process of claim 10 wherein the pressure is from about 1000 to about3000 psig and the temperature is from about 100 to 130° C.
 12. Theprocess of claim 11 wherein the amount of water is up to about 10 weightpercent, based on the weight of the reaction mixture.
 13. A single-stepprocess for manufacturing 1,3-propanediolwith CO and H₂ in a etherreaction solvent, said process being characterized by reacting areaction mixture comprising (1) ethylene oxide at a concentration fromabout 0.01 to about 30 weight percent; (2) rhodium at a molarconcentration from about 0.00001 to about 0.1 molar; (3) a phosphinehaving the formula

    PR.sub.1 R.sub.2 R.sub.3                                   III

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of aliphatic and aromatic hydrocarbon groups, the molar ratioof rhodium to phosphine being from about 10:1 to about 1:1; (4) water inan amount from about 0.00 to about 25 weight percent based on the weightof the reaction mixture; (5) CO; (6) H₂ ; wherein the molar ratio of COto H₂ is from about 10:1 to about 1:10, and wherein the reaction takesplace at a temperature from about 50 to about 200° C. under a pressurefrom about 200 to about 10,000 psig, for a period of time which issufficient to form 1,3-propanediol.
 14. The process of claim 13 whereinthe solvent is selected from the group consisting of tetraglyme,tetrahydrofuran, and a mixture of glycol polyethers of ethylene andpropylene glycols.
 15. The process of claim 13 wherein the rhodium isselected from the group consisting of rhodium metal, rhodium oxides,RhI₃, RhBr₃, RhCl₃, Rh(Acac)₃, Rh(CO)₂ Acac, Rh₆ (CO)₁₆, [RhCl(CO)₂ ]₂,and Rh(NO₃)₃.
 16. The process of claim 15 wherein the rhodium is presentat a concentration from about 0.005 to about 0.10 molar.
 17. The processof claim 16 wherein the phosphine is a trialkyl phosphine.
 18. Theprocess of claim 17 wherein the phosphine is selected from the groupconsisting of tri-isopropyl phosphine, tri-sec-butylphosphine,tri-isobutylphosphine, tri-n-butylphosphine, and tri-n-propyl phosphine.19. The process of claim 18 wherein the molar ratio of rhodium tophosphine is from about 1:2 to about 1:1.
 20. The process of claim 19wherein the ratio of H₂ :CO is from about 5:1 to about 1:1.
 21. Theprocess of claim 20 wherein the pressure is from about 1000 to about3000 psig and the temperature is from aobut 100 to 130° C.
 22. Theprocess of claim 21 wherein the amount of water is up to about 10 weightpercent, based on the weight of solvent.
 23. The process of claim 1wherein a salt of an alkali metal cation is added to the reactionmixture.
 24. The process of claim 23 wherein the salt is LiI.
 25. Theprocess of claim 23 wherein the salt is lithium acetate.
 26. The processof claim 13 wherein a salt of an alkali metal cation is added to thereaction mixture.
 27. The process of claim 26 wherein the salt is LiI.28. The process of claim 27 wherein the salt is lithium acetate.